CN110773186B - In-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide and preparation method thereof - Google Patents
In-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
- C01B17/0486—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with carbon monoxide or carbon monoxide containing mixtures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
- C01B17/0491—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with hydrogen or hydrogen-containing mixtures, e.g. synthesis gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention provides an in-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide and a preparation method thereof, wherein the in-situ catalyst comprises the following components: 10% -40% of CoO and 30% -60% of Al2O32 to 10 percent of MgO and 5 to 10 percent of Fe2O30.5 to 5 percent of La2O32% -10% of MoO3(ii) a The catalyst prepared by the method not only improves the content of hydrogen in the mixed atmosphere, but also can reduce water generated by reduction reaction and improve the hydrothermal stability of the catalyst.
Description
Technical Field
The invention belongs to the technical field of sulfur dioxide reduction for preparing sulfur, and particularly relates to an in-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide and a preparation method thereof.
Background
The emission source of sulfur dioxide in China is mainly generated by the production processes of coal burning, steel smelting, non-ferrous metal and precious metal smelting, petrochemical industry and the like; wherein the concentration is high (phi SO)2> 3%) of SO2Mainly used for preparing sulfuric acid, low concentration (phi SO)2＜1％)SO2Sulfate is generated mainly by neutralization of alkali metal or alkaline earth metal; due to the limitation of conditions such as region, transportation, production, storage and transportation, the process for preparing sulfuric acid from sulfur dioxide is not suitable for remote smelting plants, but can improve the added value of enterprise products by preparing sulfur.
The technology for recovering sulfur is divided into a direct reduction method and an indirect reduction method, wherein the direct reduction method belongs to H2And CO as a reducing agent, less by-products, relatively low temperature required for reaction, and H2And CO is used as a reducing agent, the raw materials are easy to obtain, the reaction temperature for reducing sulfur dioxide by hydrogen is lower, the number of byproducts is less, and coal gasification can be adoptedThe content of hydrogen in the generated synthesis gas is improved through a shift reaction, so that hydrogen-rich synthesis gas with lower cost is obtained, and deep reduction of sulfur dioxide is realized.
Hydrodesulfurization catalysts commonly used in industry are: Co-Mo/Al2O3、Co-W/Al2O3、Ni-Co/Al2O3The catalyst has higher activity for deep purification and desulfurization, and is more suitable for sulfur-containing gas with lower concentration (generally less than 5 percent), while the current production unit can adopt a cheap technology to enrich sulfur dioxide with higher concentration (generally more than 90 percent), the sulfur dioxide reduction reaction belongs to the reaction with great heat release, and the more suitable catalyst is required to be adopted for the sulfur dioxide reduction reaction with higher concentration;
the novel NiMoW bulk catalyst reported in U.S. Pat. Nos. 6299760 and 6156695 is a novel sulfur dioxide reduction catalyst, the preparation process of the method is complex, the NiMoW needs to form uniform and stable sulfides, the process parameters need to be strictly controlled, and the method is not easy to repeat; the catalyst disclosed in the Chinese patent CN107175108 adopts a cobalt-based sulfur dioxide reduction catalyst prepared by a traditional impregnation method, active components are not uniformly dispersed, the uniformity of impregnation of a multi-component mixed solution is difficult to control, and the catalyst is easy to have a short service life and is easy to be oxidized in a short period. The sulfur dioxide reduction catalyst is not only not well controlled in process, but also is easy to oxidize and deactivate the high-concentration sulfur dioxide raw material.
Disclosure of Invention
The invention aims to provide an in-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide and a preparation method thereof, which solve the problems that the existing sulfur dioxide reduction catalyst is not well controlled in process and is easy to oxidize and inactivate the high-concentration sulfur dioxide raw material.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides an in-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide, which comprises the following components in percentage by weight: 10% -40% of CoO, 30-60% of Al2O32 to 10 percent of MgO and 5 to 10 percent of Fe2O30.5 to 5 percent of La2O32% -10% of MoO3。
A preparation method of an in-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide comprises the following steps:
step 1, preparing a mixed solution
Mixing (1.0-3.0) mol/L of Co (NO)3)2·6H2O, (1-3) mol/L Al (NO)3)3·9H2O and (1.0-8.0) mol/L CO (NH)2)2And (0.02-0.2) mol/L Fe (NO)3)3·9H2O, (0.1-0.7) mol/L Mg (NO)3)2·6H2O and (0.01-0.0)6mol/L La (NO)3)3·nH2Mixing the O to obtain a mixed solution;
step 2, carrying out precipitation reaction on the prepared mixed solution, and then cooling, filtering and washing to obtain a precipitate;
step 3, drying and cooling the precipitate obtained in the step 2 to room temperature to obtain a cobalt-aluminum hydrotalcite-like catalyst precursor;
step 4, preparing the cobalt-aluminum hydrotalcite catalyst precursor obtained in the step 3 into slurry emulsion, and preparing the slurry emulsion and (NH)4)2MoO4The solution is mixed for ion exchange reaction, then is centrifuged, washed, dried and put in H2S/H2Roasting in the atmosphere to obtain a catalyst product for preparing sulfur by reducing sulfur dioxide.
Preferably, in step 2, the precipitation reaction is carried out by the following process:
and (2) placing the mixed solution obtained in the step (1) in a rotary evaporator, and slowly raising the temperature of the oil bath to 80-110 ℃ to perform precipitation reaction, wherein in the reaction process, 0.10mol/L ammonia water is dropwise added into the mixed solution, so that the pH value of the mixed solution is 7.5-9.0.
Preferably, in step 3, the precipitate obtained in step 2 is subjected to microwave drying at 60-90 ℃ for 0.5-4h, and then cooled to room temperature, so as to obtain the cobalt-aluminum hydrotalcite-like catalyst precursor.
Preferably, in step 4, the concentration of the slurry emulsion is (0.01-0.9) mol/L; (NH)4)2MoO4The concentration of the solution is (0.01-0.2) mol/L.
Preferably, in step 4, the process of the ion exchange reaction is: mixing the slurry emulsion with (NH)4)2MoO4And placing the mixed solution of the solution in a rotary evaporator, carrying out ion exchange reaction for 5-12h at the temperature of 80-160 ℃, and dropwise adding 0.10mol/L ammonia water into the mixed solution in the reaction process to ensure that the pH value of the mixed solution is 8-10.0.
Preferably, in step 4, after ion exchange, the mixture is centrifuged and washed, and then microwave dried at 60-90 ℃ for 0.5-4H to obtain a dried substance, and the dried substance is placed in a tube furnace and subjected to H2S/H2In the atmosphere, roasting and vulcanizing in situ at 400-600 ℃ for 4-8h to obtain the catalyst product for preparing sulfur by reducing sulfur dioxide.
Compared with the prior art, the invention has the beneficial effects that:
according to the in-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide, the generated cobalt-aluminum hydrotalcite structure has a larger specific surface area compared with a traditional catalyst carrier, so that the in-situ catalyst can effectively adsorb sulfur dioxide in the catalytic reaction process; by regulating the content of auxiliary agents such as Fe, Mg, La and the like, the H pair of the catalyst is properly regulated and controlled2And the adsorption capacity of CO, particularly the introduction of the auxiliary agent provides a catalytic active center for CO conversion reaction, so that the content of hydrogen in the mixed atmosphere is improved, the water generated by the reduction reaction can be reduced, and the hydrothermal stability of the catalyst is improved.
The invention provides a preparation method of an in-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide, which is implemented by CO (NH)2)2Slowly hydrolyzing at 90-120 deg.C in rotary evaporator to provide OH needed for precipitation-And CO2-Uniform [ Co ] is produced1-x 2+Alx 3+(OH)2]x+(CO3)x/2 2-Precipitating to form a component with a layered hydrotalcite-like structure, and roasting to obtain a cobalt-aluminum composite oxide; the hydrotalcite-like structure is not only beneficial to the dispersion of cobalt components, but also has strong interaction between cobalt and aluminum, can effectively prevent the sintering and hydrothermal oxidation of the cobalt components, and has good hydrothermal stability. After the ion exchange is finished, H is introduced into the catalyst semi-finished product in a tubular furnace2S/H2And the active center of the generated metal sulfide is dispersed more uniformly and has better activity after atmosphere roasting.
Detailed Description
The present invention is described in further detail below.
The in-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide comprises, by weight, 10% -40% of CoO and 30% -60% of Al2O32 to 10 percent of MgO and 5 to 10 percent of Fe2O30.5 to 5 percent of La2O32% -10% of MoO3。
The invention provides a preparation method of an in-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide, which comprises the following steps:
step 1, preparing a mixed solution
Mixing (1.0-3.0) mol/L of Co (NO)3)2·6H2O, (1-3) mol/L Al (NO)3)3·9H2O and (1.0-8.0) mol/L CO (NH)2)2And (0.02-0.2) mol/L Fe (NO)3)3·9H2O, (0.1-0.7) mol/L Mg (NO)3)2·6H2O and (0.01-0.0)6mol/L La (NO)3)3·nH2Mixing the O to obtain a mixed solution;
step 2, transferring the prepared mixed solution into a rotary evaporator, slowly increasing the oil bath temperature to 80-110 ℃ under the condition of continuous rotation, dropwise adding 0.10mol/L ammonia water and maintaining the pH value of the mother solution to be 7.5-9.0, and carrying out precipitation reaction; after the precipitation reaction, lifting an evaporator, removing the oil bath pot, continuously rotating and cooling the mother liquor at room temperature for 2-4h, and performing suction filtration and washing to obtain a precipitate; drying the precipitate at 60-90 deg.C for 0.5-4h with microwave, and cooling to room temperature to obtain cobalt aluminum hydrotalcite catalyst precursor;
step 3, preparing the prepared catalyst precursor into slurry emulsion with the concentration of (0.01-0.9) mol/L, and preparing (0.01-0.2) mol/L of (NH)4)2MoO4Solution of, wherein (NH)4)2MoO4The mass ratio of the solution to the cobalt-aluminum hydrotalcite catalyst precursor is 1 (10-15), the solution and the emulsion are mixed in a rotary evaporator at the temperature of 80-160 ℃ for ion exchange reaction for 5-12h, 0.10mol/L ammonia water is dropwise added, and the pH value of the mother solution is maintained between 8-10.0; after the exchange is finished, centrifuging, washing, microwave drying at 60-90 ℃ for 0.5-4H, passing through a tube furnace, and performing microwave drying in H2S/H2Roasting and vulcanizing in situ at 400-600 ℃ for 4-8h under the atmosphere to obtain the catalyst product for preparing sulfur by reducing sulfur dioxide.
Example one
135g of Co (NO) are weighed out3)2·6H2O, 300g of Al (NO)3)3·9H2O, 15g of Fe (NO)3)3·9H2O, 32g of Mg (NO)3)2·6H2O, 1.5g of La (NO)3)3·nH2O and 180g of CO (NH)2)2The mixed solution of (1); transferring the mixed solution into a rotary evaporator, slowly increasing the oil bath temperature to 90 ℃ under the condition of continuous rotation, dropwise adding 0.10mol/L ammonia water and maintaining the pH value of mother liquor between 8.0, and carrying out precipitation reaction for 3 hours; after the precipitation reaction, lifting the evaporator, removing the oil bath pot, continuously rotating and cooling the mother liquor for 2 hours at room temperature, and performing suction filtration and washing to obtain a precipitate; drying the precipitate at 90 ℃ for 2h by microwave, and cooling to room temperature to obtain a cobalt-aluminum hydrotalcite-like catalyst precursor for later use;
weighing 140g of the precursor of the cobalt-aluminum hydrotalcite-like catalyst prepared above, adding the precursor into a 500ml beaker, adding 300ml of deionized water to prepare slurry emulsion, transferring the slurry emulsion into a rotary evaporator, and weighing 11g of (NH)4)2MoO4Adding the mixture into the emulsion, carrying out ion exchange reaction at 150 ℃ for 12 hours, dropwise adding 0.10mol/L ammonia water, and maintaining the pH value of the mother solution at 8.0; separation deviceAfter the completion of the sub-exchange, the mixture is centrifuged, washed and microwave dried at 90 ℃ for 0.5H, and then passed through a tube furnace in H2S/H2Roasting and vulcanizing in situ for 4 hours at 600 ℃ in the atmosphere to obtain a catalyst product for preparing sulfur by reducing sulfur dioxide;
example two
Weighing 150g of Co (NO)3)2·6H2O, 320g of Al (NO)3)3·9H2O, 18g of Fe (NO)3)3·9H2O, 35g of Mg (NO)3)2·6H2O, 3.5g La (NO)3)3·nH2O and 190g of CO (NH)2)2The mixed solution of (1); transferring the mixed solution into a rotary evaporator, slowly increasing the oil bath temperature to 100 ℃ under the condition of continuous rotation, dropwise adding 0.10mol/L ammonia water and maintaining the pH value of mother liquor between 8.0, and carrying out precipitation reaction; after the precipitation reaction, lifting the evaporator, removing the oil bath pot, continuously rotating and cooling the mother liquor for 2 hours at room temperature, and performing suction filtration and washing to obtain a precipitate; drying the precipitate at 0 ℃ for 0.5h by microwave, and cooling to room temperature to obtain a cobalt-aluminum hydrotalcite-like catalyst precursor for later use;
weighing 160g of the precursor of the cobalt aluminum hydrotalcite-like catalyst prepared above, adding the precursor into a 500ml beaker, adding 300ml of deionized water to prepare slurry emulsion, transferring the slurry emulsion into a rotary evaporator, and weighing 14g of (NH)4)2MoO4Adding the mixture into the emulsion, carrying out ion exchange reaction for 12 hours at 140 ℃, dropwise adding 0.10mol/L ammonia water, and maintaining the pH value of the mother solution between 9.0; after the exchange is finished, centrifuging, washing, microwave drying at 0 ℃ for 0.5H, passing through a tube furnace, and performing microwave drying on the obtained product in H2S/H2Roasting and vulcanizing at 500 ℃ in situ for 4h under the atmosphere to obtain a catalyst product for preparing sulfur by reducing sulfur dioxide;
EXAMPLE III
Weighing 100g of Co (NO)3)2·6H2O, 230g of Al (NO)3)3·9H2O, 18g of Fe (NO)3)3·9H2O, 38g of Mg (NO)3)2·6H2O, 2.4g of La (NO)3)3·nH2O and 170g of CO (NH)2)2The mixed solution of (1); transferring the mixed solution into a rotary evaporator, slowly increasing the oil bath temperature to 80-110 ℃ under the condition of continuous rotation, dropwise adding 0.10mol/L ammonia water and maintaining the pH value of mother liquor between 9.0, and carrying out precipitation reaction; after the precipitation reaction, lifting the evaporator, withdrawing the oil bath pot, continuously rotating and cooling the mother liquor for 3 hours at room temperature, and carrying out suction filtration and washing to obtain a precipitate; drying the precipitate at 90 ℃ for 0.5h by microwave, and cooling to room temperature to obtain a cobalt-aluminum hydrotalcite-like catalyst precursor for later use;
weighing 120g of the precursor for preparing the cobalt-aluminum hydrotalcite-like catalyst, adding the precursor into a 500ml beaker, adding 300ml of deionized water to prepare slurry emulsion, transferring the slurry emulsion into a rotary evaporator, and weighing 14g of (NH)4)2MoO4Adding the mixture into the emulsion, carrying out ion exchange reaction for 10 hours at 150 ℃, dropwise adding 0.10mol/L ammonia water, and maintaining the pH value of the mother solution between 10.0; after the exchange is finished, centrifuging, washing, drying for 0.5H at 90 ℃ by microwave, passing through a tube furnace, and purifying in H2S/H2Roasting and vulcanizing in situ for 4-8h at 600 ℃ in the atmosphere to obtain a catalyst product for preparing sulfur by reducing sulfur dioxide;
example four
Weighing 125g of Co (NO)3)2·6H2O, 280g of Al (NO)3)3·9H2O, 20g of Fe (NO)3)3·9H2O, 40g of Mg (NO)3)2·6H2O, 3.6g of La (NO)3)3·nH2O and 185g of CO (NH)2)2The mixed solution of (1); transferring the mixed solution into a rotary evaporator, slowly increasing the oil bath temperature to 110 ℃ under the condition of continuous rotation, dropwise adding 0.10mol/L ammonia water and maintaining the pH value of mother liquor between 8.0, and carrying out precipitation reaction; after the precipitation reaction, lifting the evaporator, removing the oil bath pot, continuously rotating and cooling the mother liquor for 2 hours at room temperature, and performing suction filtration and washing to obtain a precipitate; drying the precipitate at 90 ℃ for 1h by microwave, and cooling to room temperature to obtain a cobalt-aluminum hydrotalcite-like catalyst precursor for later use;
weighing the prepared cobalt-aluminum hydrotalcite catalyst150g of the precursor was added to a 500ml beaker, 300ml of deionized water was added to prepare a slurry emulsion, which was transferred to a rotary evaporator and 16g of (NH) was weighed4)2MoO4Adding the mixture into the emulsion, carrying out ion exchange reaction for 10 hours at 130 ℃, dropwise adding 0.10mol/L ammonia water, and maintaining the pH value of the mother solution between 9.0; after the exchange is finished, centrifuging, washing, drying for 0.5H at 90 ℃ by microwave, passing through a tube furnace, and purifying in H2S/H2Roasting and vulcanizing in situ for 5h at 600 ℃ in the atmosphere to obtain a catalyst product for preparing sulfur by reducing sulfur dioxide;
EXAMPLE five
Weighing 80g of Co (NO)3)2·6H2O, 180g of Al (NO)3)3·9H2O, 13g of Fe (NO)3)3·9H2O, 31g of Mg (NO)3)2·6H2O, 4.5g La (NO)3)3·nH2O and 150g of CO (NH)2)2The mixed solution of (1); transferring the mixed solution into a rotary evaporator, slowly increasing the oil bath temperature to 110 ℃ under the condition of continuous rotation, dropwise adding 0.10mol/L ammonia water and maintaining the pH value of mother liquor between 9.0, and carrying out precipitation reaction; after the precipitation reaction, lifting the evaporator, withdrawing the oil bath pot, continuously rotating and cooling the mother liquor for 4 hours at room temperature, and carrying out suction filtration and washing to obtain a precipitate; drying the precipitate at 90 ℃ for 0.5h by microwave, and cooling to room temperature to obtain a cobalt-aluminum hydrotalcite-like catalyst precursor for later use;
weighing 100g of the precursor of the cobalt aluminum hydrotalcite-like catalyst prepared above, adding the precursor into a 500ml beaker, adding 300ml of deionized water to prepare slurry emulsion, transferring the slurry emulsion into a rotary evaporator, and weighing 12g of (NH)4)2MoO4Adding the mixture into the emulsion, carrying out ion exchange reaction for 12 hours at 140 ℃, dropwise adding 0.10mol/L ammonia water, and maintaining the pH value of the mother solution between 10.0; after the exchange is finished, centrifuging, washing, drying for 0.5H at 90 ℃ by microwave, passing through a tube furnace, and purifying in H2S/H2Roasting and vulcanizing at 400 ℃ in situ for 8h under the atmosphere to obtain a catalyst product for preparing sulfur by reducing sulfur dioxide;
EXAMPLE six
Weighing 60g of Co (NO)3)2·6H2O, 150g of Al (NO)3)3·9H2O, 10g of Fe (NO)3)3·9H2O, 24g of Mg (NO)3)2·6H2O, 4g La (NO)3)3·nH2O and 120g of CO (NH)2)2The mixed solution of (1); transferring the mixed solution into a rotary evaporator, slowly increasing the oil bath temperature to 110 ℃ under the condition of continuous rotation, dropwise adding 0.10mol/L ammonia water and maintaining the pH value of mother liquor between 9.0, and carrying out precipitation reaction; after the precipitation reaction, lifting the evaporator, withdrawing the oil bath pot, continuously rotating and cooling the mother liquor for 4 hours at room temperature, and carrying out suction filtration and washing to obtain a precipitate; drying the precipitate at 90 ℃ for 0.5h by microwave, and cooling to room temperature to obtain a cobalt-aluminum hydrotalcite-like catalyst precursor for later use;
weighing 80g of the precursor of the cobalt-aluminum hydrotalcite-like catalyst prepared above, adding the precursor into a 500ml beaker, adding 300ml of deionized water to prepare slurry emulsion, transferring the slurry emulsion into a rotary evaporator, and weighing 10g of (NH)4)2MoO4Adding the mixture into the emulsion, carrying out ion exchange reaction for 12 hours at 150 ℃, dropwise adding 0.10mol/L ammonia water, and maintaining the pH value of the mother solution between 10.0; after the exchange is finished, centrifuging, washing, drying for 0.5H at 90 ℃ by microwave, passing through a tube furnace, and purifying in H2S/H2Roasting and vulcanizing in situ for 6h at 600 ℃ in the atmosphere to obtain a catalyst product for preparing sulfur by reducing sulfur dioxide;
activity evaluation
Crushing and screening the finished catalyst to 20-40 meshes, and filling the catalyst into a fixed bed reactor at an airspeed of 6000h-1Wherein the raw material gas comprises SO: h2：CO：CO2：N220%: 40%: 3%: 30%: 7% and the activity data at the evaluation temperature of each example are given in Table 1:
TABLE 1 catalytic Activity data at different temperatures
Claims (4)
1. The preparation method of the in-situ catalyst for preparing the sulfur by reducing the high-concentration sulfur dioxide is characterized by comprising the following steps of:
the in-situ catalyst comprises the following components in percentage by weight: 10% -40% of CoO and 30% -60% of Al2O32 to 10 percent of MgO and 5 to 10 percent of Fe2O30.5 to 5 percent of La2O32% -10% of MoO3；
Step 1, preparing a mixed solution
Mixing (1.0-3.0) mol/L of Co (NO)3)2·6H2O, (1-3) mol/L Al (NO)3)3·9H2O and (1.0-8.0) mol/L CO (NH)2)2And (0.02-0.2) mol/L Fe (NO)3)3·9H2O, (0.1-0.7) mol/L Mg (NO)3)2·6H2O and (0.01-0.0)6mol/L La (NO)3)3·nH2Mixing the O to obtain a mixed solution;
step 2, carrying out precipitation reaction on the prepared mixed solution, and then cooling, filtering and washing to obtain a precipitate;
step 3, drying and cooling the precipitate obtained in the step 2 to room temperature to obtain a cobalt-aluminum hydrotalcite-like catalyst precursor;
step 4, preparing the cobalt-aluminum hydrotalcite catalyst precursor obtained in the step 3 into slurry emulsion, and preparing the slurry emulsion and (NH)4)2MoO4The solution is mixed for ion exchange reaction, then is centrifuged, washed, dried and put in H2S/H2Roasting in the atmosphere to obtain a catalyst product for preparing sulfur by reducing sulfur dioxide, wherein (NH)4)2MoO4The mass ratio of the solution to the precursor of the cobalt-aluminum hydrotalcite-like catalyst is 1: (10-15);
wherein, in the step 2, the precipitation reaction process comprises the following steps:
placing the mixed solution obtained in the step 1 in a rotary evaporator, slowly raising the temperature of an oil bath to 80-110 ℃ for precipitation reaction, wherein in the reaction process, dropwise adding 0.10mol/L ammonia water into the mixed solution to ensure that the pH value of the mixed solution is 7.5-9.0;
and 3, drying the precipitate obtained in the step 2 at the temperature of 60-90 ℃ for 0.5-4h by using microwaves, and cooling to room temperature to obtain the cobalt-aluminum hydrotalcite-like catalyst precursor.
2. The method for preparing an in-situ catalyst for sulfur production by reduction of sulfur dioxide with high concentration according to claim 1, wherein in step 4, the concentration of the slurry emulsion is (0.01-0.9) mol/L; (NH)4)2MoO4The concentration of the solution is (0.01-0.2) mol/L.
3. The method for preparing the in-situ catalyst for preparing the sulfur by reducing the high-concentration sulfur dioxide according to the claim 1, wherein the ion exchange reaction process in the step 4 is as follows: mixing the slurry emulsion with (NH)4)2MoO4And placing the mixed solution of the solution in a rotary evaporator, carrying out ion exchange reaction for 5-12h at the temperature of 80-160 ℃, and dropwise adding 0.10mol/L ammonia water into the mixed solution in the reaction process to ensure that the pH value of the mixed solution is 8-10.0.
4. The method for preparing the in-situ catalyst for preparing the sulfur by the reduction of the high-concentration sulfur dioxide according to the claim 1, wherein the ion exchange is completed in the step 4, the product is centrifuged and washed, then the product is dried by microwave for 0.5 to 4 hours at the temperature of 60 to 90 ℃ to obtain the dried product, and the dried product is placed in a tube furnace and subjected to H2S/H2In the atmosphere, roasting and vulcanizing in situ at 400-600 ℃ for 4-8h to obtain the catalyst product for preparing sulfur by reducing sulfur dioxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911136624.5A CN110773186B (en) | 2019-11-19 | 2019-11-19 | In-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide and preparation method thereof |
| PCT/CN2020/125518 WO2021098489A1 (en) | 2019-11-19 | 2020-10-30 | In-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide, and preparation method for in-situ catalyst |
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| CN201911136624.5A CN110773186B (en) | 2019-11-19 | 2019-11-19 | In-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide and preparation method thereof |
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| CN115282958A (en) * | 2022-01-12 | 2022-11-04 | 昆明理工大学 | Catalyst for catalyzing carbon monoxide to reduce sulfur dioxide and preparation method thereof |
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| CN107175108A (en) * | 2017-07-10 | 2017-09-19 | 中国科学院过程工程研究所 | A kind of cobalt series catalyst that sulphur processed is reduced for sulfur dioxide in flue gas and its production and use |
| CN107376925A (en) * | 2017-07-21 | 2017-11-24 | 中国华能集团公司 | A kind of low temperature high activity carbon dioxide methanation catalyst and preparation method thereof |
| CN110237680A (en) * | 2019-06-17 | 2019-09-17 | 中国华能集团有限公司 | A kind of temperature equalization system and technique of synthesis gas reduction sulfur dioxide |
| CN110302784A (en) * | 2019-07-31 | 2019-10-08 | 山东大学 | Grain slag base CO catalysis reduction sulfur dioxide prepares the catalyst and preparation method and application of sulphur |
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| US6299760B1 (en) * | 1999-08-12 | 2001-10-09 | Exxon Research And Engineering Company | Nickel molybodtungstate hydrotreating catalysts (law444) |
| CN1099902C (en) * | 1999-12-08 | 2003-01-29 | 中国科学院山西煤炭化学研究所 | Catalyst for treating SO2 in waste gas and its application method |
| CN101745399A (en) * | 2008-12-02 | 2010-06-23 | 山东迅达化工集团有限公司 | Selective reduction catalyst used for recovering sulfur, preparation method and application thereof |
| CN105251512B (en) * | 2015-09-16 | 2017-04-05 | 福州大学化肥催化剂国家工程研究中心 | Transformation catalyst with cobalt magnesia-alumina hydrotalcite as predecessor and preparation method thereof |
| CN110773186B (en) * | 2019-11-19 | 2021-09-17 | 中国华能集团有限公司 | In-situ catalyst for preparing sulfur by reducing high-concentration sulfur dioxide and preparation method thereof |
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| CN107175108A (en) * | 2017-07-10 | 2017-09-19 | 中国科学院过程工程研究所 | A kind of cobalt series catalyst that sulphur processed is reduced for sulfur dioxide in flue gas and its production and use |
| CN107376925A (en) * | 2017-07-21 | 2017-11-24 | 中国华能集团公司 | A kind of low temperature high activity carbon dioxide methanation catalyst and preparation method thereof |
| CN110237680A (en) * | 2019-06-17 | 2019-09-17 | 中国华能集团有限公司 | A kind of temperature equalization system and technique of synthesis gas reduction sulfur dioxide |
| CN110302784A (en) * | 2019-07-31 | 2019-10-08 | 山东大学 | Grain slag base CO catalysis reduction sulfur dioxide prepares the catalyst and preparation method and application of sulphur |
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